Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L21/00—Compositions of unspecified rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/16—Ethene-propene or ethene-propene-diene copolymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
  • B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
  • B29K2105/10—Cords, strands or rovings, e.g. oriented cords, strands or rovings
  • B29K2105/101—Oriented
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2031/00—Other particular articles
  • B29L2031/08—Blades for rotors, stators, fans, turbines or the like, e.g. screw propellers
  • B29L2031/087—Propellers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment

Definitions

• the present invention relates to a reinforced resin composition capable of providing a molded article having excellent dimensional stability as well as excellent creep properties and breaking strength among mechanical and physical properties.
• a reinforced resin composition capable of providing a molded article having excellent dimensional stability as well as excellent creep properties and breaking strength among mechanical and physical properties.
• the present invention when used to agitate or transport a fluid, it is difficult to break down to a high rotation speed range, and it is difficult to exhibit a clipping phenomenon due to rotation. It concerns a propeller-type fan with high stability. Background technology
• the glass fiber reinforced polyrefin composition in whole or in part, Crystalline modified polyolefin with 10% by weight or less of polar vinyl monomer 40 to 85 parts by weight, glass fiber 5 or 5 0 'parts by weight and 5 to 35 parts by weight (total 100 parts by weight) of linear amorphous rubber-like elastic material are mixed uniformly.
• This prior art 1 is similar in terms of the components of the present invention and their weight ratio, but is completely different from the purpose of the present invention.
• the square plate created by injection molding was evaluated as a test piece, and of course, there was no way to carry out a rotation test. Therefore, neither the rotational fracture strength nor the rotational cleaving amount is mentioned.
• a crystalline homopolypropylene modified with a graphite by an unsaturated polar vinyl monomer is used as a reinforced polypropylene composition having improved abrasion resistance.
• the purpose of this prior art 2 is to improve the wear resistance of the molded article, and as a result, a disk was prepared as a test piece by injection molding. However, only the amount of wear of the taper is measured.
• the object of the present invention is not to make a rotating body with blades, but also to try to find the breaking limit by the rotation and to measure the creep deformation by the rotation. I have not been left.
• a glass fiber reinforced polyolefin resin composition comprising: (a) a polypropylene resin having a melt index of 5 g / 10 minutes or more; 45 to 85% by weight-(b) Density of 0.89 to 0.93 g / cm3 Maleodex index force ⁇ 5 g / 10 min. 5 to 25% by weight of low-density polyethylene having an MI ratio of 0.5 to 5, (c) the fiber diameter and the average fiber length in the molded product 1 to 6 mra It is disclosed that a specific amount of modified polyolefin is added to a base material comprising a specific amount of glass fiber.
• Prior Art 3 positions the blend of ethylene-propylene copolymer elastomer as harmful. That is, in Comparative Example 2, a composition containing "10% by weight" of "EPR" is described. Also, when molding a high-speed rotating device such as a propeller-type fan according to the prescription, the molded product has a high level of rotational breaking strength and a high rotational speed. It does not mention at all that even a slight creep deformation occurs.
• the above-mentioned literature relates to the load generated by the rotation of the molded article and the creep deformation of the molded article caused by the load. It was not mentioned.
• a rotary member for example, a propeller-type fan was manufactured by using such a conventional fiber-reinforced resin composition using short fibers. At this time, the rotation of the fan, especially in the high rotation region, causes the deformation of the cleaving, and as a result, the rotation is destroyed, and as a result, the predetermined function is not performed.
• the present inventor has used a long fiber at the beginning. Injection molding of long fiber reinforced pillars created using newly developed means to create long fiber reinforced pillars contained in resin matrix with length A long fiber reinforced columnar body and a rotating member that can be used as a molding material to form a rotating member that does not cause creep or breakage due to the load in the rotational direction by an appropriate molding method.
• a fan-type fan with particularly strict requirements. That is, the present invention provides various configurations defined in the following “Basic configuration of columnar body”, “Improved configuration 1 of columnar body” to “Improved configuration of columnar body”, and “Basic configuration of molded article”. Consists of
• the long fiber reinforced material (B) has a length substantially equal to the average fiber length, and is aligned in the long axis direction of the long fiber reinforced columnar body (D). Fiber-reinforced columns (D).
• the long fiber reinforced columnar body (D) according to “Basic configuration of columnar body”, wherein the long fiber reinforced material (B) has an average fiber length of 5 to 25.
• the organic silane-based compound as a modifier is selected from aminosilane, epoxyxylan, vinylilane and methacryloxysilan1 Long fiber reinforced columnar bodies (D) described in “Basic configuration of columnar bodies” and “Improved configuration 1 of columnar bodies” to “Improved configuration 4 of columnar bodies” of at least one kind.
• the propylene crystalline resin that is the base material of the modified propylene crystalline resin (A) is a propylene-ethylene crystalline copolymer.
• Elastomer (C) is an ethylene-propylene copolymer copolymer and an ethylene-propylene-non-conjugated gen copolymer copolymer.
• ⁇ Basic columnar structure, '' which is one or more olefin-based rasters selected from the stoma Long-fiber reinforced columnar bodies (D) described in "Structure of the column” and “Improved configuration 1 of the columnar body” to "Improved configuration 7 of the columnar body".
• the non-conjugated gen in the elastomer (C) is 5-ethylidene-2-norbornane, 1,4-hexagene and disixene Long fiber reinforcement described in “Basic configuration of pillars” and “Improved configuration of pillars 1”-“Improved configuration of pillars 8”, which is one or more types selected from the mouth pen Column (D) 0
• the long fiber reinforced columnar body (D) is manufactured by injection molding the long fiber reinforced columnar body (D).
• the long fiber reinforced material (B) is substantially aligned in the long axis direction of the long fiber reinforced column (D), and the length of the long fiber reinforced column (D) is Substantially the same — a propeller fan of the same length.
• FIG. 1A is a schematic plan view showing a preferred embodiment of a propeller type fan according to the present invention.
• FIG. 1B is a schematic side view of the embodiment of the present invention.
• the long fiber reinforced columnar body (D) is prepared from a specific modified propylene crystalline resin (A), a long fiber reinforced material (B), and an elastomer (C). Become. First, each component (A) to (C) will be described.
• the modified propylene crystalline resin (A) contained in the reinforced columnar body of the present invention refers to an organic silane-based compound or a modified poly (propylene) base material as a modifier. Crystalline polypropylene modified with unsaturated carboxylic acid or its anhydride, or non-modified crystalline polypropylene It is a composition (mixture) with ren.
• the crystalline polypropylene base material is a crystalline copolymer of propylene and a crystalline copolymer of propylene with one or more other ⁇ -olefins.
• Any polymer may be used, and may be a crystalline homopolymer of propylene and a crystalline copolymer of propylene and one or more other ⁇ -olefins.
• the composition may be
• the organic compound forming the modified propylene crystalline polymer (A) in the present invention is selected from amino silane, epoxy silane, bulsilane, and metacryloxyl silane One or more species can be mentioned.
• the unsaturated carboxylic acid forming the modified propylene crystalline polymer (A) in the present invention include acrylic acid and methacrylic acid.
• the anhydride may be at least one of maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, norbornane dicarboxylic anhydride, and the like. Can be mentioned. Of these, maleic anhydride has the best practical performance, and derivatives of these acids may be used. .
• the amount of the modifying agent contained as a graphite component in the modified propylene crystalline resin (A) in the long fiber reinforced composition is determined by the weight of the base resin. Usually, 0.01 to 1% by weight, preferably 0.05 to 0.5% by weight, will suffice for normal purposes.
• the component (A) is a combination (combined use) of a modified resin and a non-modified resin, the modified resin is contained in the modified resin as a graphitic component. It is necessary to set the amount of the agent within the above range in the combination system.
• the long fiber reinforced material (B) constituting the long fiber reinforced columnar body (D) of the present invention usually has an average fiber length of 3 to 30 mm, preferably 5 to 25 mm.
• the average diameter of the single fibers is 3 to 21 nm, preferably 9 to 21 // m, and they are about 500 to 40000 bundles. Provided. This convergence is commonly referred to as a rowing or end. Further, two or more of these rovings and the like can be used in a combined form.
• the long fiber reinforcing material (B) is aligned substantially parallel to the long axis of the columnar body (B), and its average length is substantially equal to the length of the columnar body. Same—must be the same.
• Such a long-fiber reinforced material (B) is formed by forming a pillar state by a method described below using a fiber material (fiber bundle) provided in an endless form. can get.
• Endless fibers that meet the above prerequisites include, for example, glass fibers, carbon fibers, synthetic resin fibers, and artificial fibers such as metal fibers.
• glass fiber is the most widely used fiber reinforced material in terms of its physical properties and price.
• the disadvantage is that it is relatively heavy (unfavorable in specific strength), easily broken, and vulnerable to alkaline.
• carbon fiber that does not make these problems from the beginning, especially those with the highest specific strength. There are almost no applications that emphasize specific strength over price. Its merits are fully demonstrated for aircraft, high-speed vehicles or high-speed rotating equipment.
• the present invention will be described by selecting the most useful glass fiber among these fiber reinforcing materials for ordinary use.
• the material of the glass fiber selected as a typical long fiber reinforcing material (B) constituting the long fiber reinforced columnar body (D) of the present invention is usually a hard glass (commonly referred to as “E glass”). This is a squid glass known as "S”.
• the elastomer (C) constituting the long fiber reinforced columnar body (D) of the present invention is usually referred to as a "gom-like material" in that it is a low crystalline or amorphous soft substance. In many cases.
• the elastomer (C) in the long fiber reinforced columnar body (D) of the present invention is soluble in or compatible with the crystalline propylene polymer as the base material. It is necessary that the polymer has an affinity to such an extent that it does not cause separation between the formed interfaces while being present as a discontinuous phase in the polymer.
• Oral-based elastomers are generally defined as ethylene and one or more other ⁇ -olefins, especially those in propylene and 1-butene.
• a low-crystalline or non-crystalline elastic material formed by copolymerization with one or more kinds, and further obtained by adding a small amount of non-conjugated diene as a third component to the copolymer. It is a copolymer of the original or higher.
• ethylene-propylene copolymer elastomer ( ⁇ ⁇ ⁇ ;), ethylene-propylene-non-conjugated gen copolymer elastomer (EPD-II), Ethylene-1-butene copolymer Elastomer ( ⁇ - ⁇ ); Ethylene-1-butene non-conjugated diene copolymer
• Elastomer Elastomer (EBDM)
• Ethylene-Propylene-1-1-Butene-Non-conjugated Diene Copolymer Elastomer (EPBD III) is also mentioned. I can do it.
• the one used as a non-conjugated gen is usually 5-ethylidino-2-rubonolene (( ⁇ ⁇ ) or 1,4-hexahexene.
• the dicyclopenta-yen (DCPD) was also used.
• the long fiber reinforced composition for forming the long fiber reinforced columnar body (D) of the present invention comprises the long fiber reinforced material (B) and the above-mentioned long fiber reinforced material (B) in the modified propylene crystalline resin (A).
• the long fiber reinforced columnar body (D) of the present invention In order to suitably mold the long fiber reinforced columnar body (D) of the present invention, the long fiber reinforced columnar body (D) must be aligned substantially parallel to the long axis of the manufactured columnar body and have substantially the same length as the columnar body. It must be possible to uniformly disperse the reinforcing fibers (C) in the resin component.
• the most prominent molding method that can achieve this state is the continuous continuous fiber impregnation method (abbreviated as follows) that can uniformly impregnate the resin component into the opened long fiber bundle.
• the melt formed from the above-mentioned modified propylene crystalline resin (A) and elastomer (c) can be mentioned.
• the open fiber impregnation tank also called “drawing molding device”.
• a long fiber roving is separately introduced from the raw material of the long fiber roving into the opening and impregnating tank.
• this opening impregnation bath a plurality of opening pins having a long axis substantially perpendicular to the traveling direction of the molten resin and the long fiber bundle are arranged along the traveling direction.
• the pins are spaced apart from each other so as to have a staggered arrangement when viewed from the axial direction, and all are kept immersed in the molten resin. You.
• the separately introduced filament opening of the long fiber is turned while contacting the peripheral surface of the first opening pin and does not contact the peripheral surface of the second opening pin.
• Endless long fibers that are repeatedly opened and run, meandering, are gradually opened, are impregnated with molten resin between the fibers, and are evenly opened.
• a reinforced endless resin strand (reinforced resin strand) is produced. If this endless reinforced resin strand is cut to a predetermined length after cooling, a long fiber reinforcing material (B) aligned substantially in parallel with the long axis direction of the columnar body is formed.
• a long fiber reinforced columnar body (D) having substantially the same length as the length is obtained.
• the propeller type fan according to the present invention was manufactured by using the long fiber reinforced columnar body (D) described above as a material and subjecting the same to injection molding.
• the propeller-type fan (F) shown in FIGS. 1A and 1B has a long fiber-reinforced column (D) that is screwed by the screwdriver to the full length (L).
• LZD the ratio
• the compression ratio is 1.8
• the four-bladed propeller type fan (F) shown in FIG. 1A is for counterclockwise rotation in the figure.
• the blades (blades) 11, 12, 13, and 14 extend from the circumference of the core shaft 1 in the radial direction.
• Each of the blades is of a bean type, and has a minimum width at a position where it rises from the core shaft 1 (not shown).
• Each crossing of the wings 1 1 to 1 4 The surface is substantially spindle-shaped, and has a thin edge at the periphery, etc., and the minimum thickness 11b is located at the tip in the rotation direction of the blade.
• the maximum thickness portion 1Id is located in a region where the radius of the blade 11 is orthogonal to the tangent to the periphery thereof and in a region sandwiching the radius.
• the propeller type fan (F) having such a shape is generated by rotation due to the use of the long fiber reinforcing material (B) according to the present invention. Creep or rotational destruction due to less weight is effectively prevented.
• the cleavage or rotational disruption of the propeller-type fan (F) according to this embodiment is performed using 11b and 11d as test sites. Can be measured.
• the above description is, of course, applicable to the other blades 12, 13, and 14.
• FIG. 1B shows the propeller type fan (F) of the present invention laterally, that is, in the direction perpendicular to the rotation axis, in particular, from the direction indicated by the arrow V in FIG. 1A. It is a side view drawing of.
• h is a convenient expression for indicating the positional relationship in the drawing, from the part 43 d (corresponding to 11 d of the blade 11) to the lower end surface of the core shaft 1 (“up, down, left, right” etc.).
• b is the distance from the part 13b (corresponding to 11b of the blade 11) to the horizontal plane.
• test method the amount of deformation, and the strength were measured by the following methods.
• the propeller type fan with four blades in Fig. 1 (diameter 450 mm: minimum blade thickness 0.5 mm and maximum blade thickness 4.0 mra) is rotated.
• the rotation speed at the time of failure occurs is referred to as “rotational failure strength”.
• Fig. 1 Deformation of blade height after propeller type fan of A and B is rotated at 100 rpm for 100 Oh in a thermostat at 65 ° C. The amount was defined as “the amount of rotational creep deformation”.
• the total content of ethylene components is 9.0% by weight, and the crystal melting point (Tm) is 1 60 ° C and MFR (230 ° C; 2.16 kgf) 2.6 g C Omin,
• Ethylene-propylene amorphous copolymer (rubber-like elastic material): Ethylene component content 74% by weight, MI (190 ° C; 2.161 ⁇ gf) 3.2 g / 10 min and Mooney viscosity [ML 1 + 4 (100 ° C)] 24.
• DS (:) differential scanning calorimeter
• the above resin mixture 1 and polyethylene propylene copolymer elastomer (abbreviated as “EPM”) were used as a resin mixture (product) )
• EPM polyethylene propylene copolymer elastomer
• melted 250 ° C
• Table 1 shows the properties of the obtained propeller fan. Comparative Examples 1 and 2
• the modified polymer was used instead of the resin mixture
• a reinforced columnar body (reinforced pellet) was manufactured in the same manner as in the example.
• Table 1 shows the composition, properties and properties of the propeller type fan manufactured from the composition and properties.
• the above-mentioned resin mixture 1 and the styrene-propylene copolymer copolymer are stirred and mixed in a helical mixer (trade name).
• a resin-elastomer mixture was obtained.
• a predetermined amount of the obtained mixture is charged from the first supply supply port of the extruder equipped with a vent suction mechanism, and glass short fibers (average fiber thickness of 13 / m3) are supplied from the second supply port.
• a predetermined amount of a chopped strand with an average fiber length of 3.0 mm) is charged and melted and kneaded while suctioning the reinforced composite.
• the obtained strand was cut (average length 3 mm) and granulated.
• the obtained modified polypropylene was the same as that of the example and had the same MFR (230 ° C; 2.16 k gf) at 130 g / l O min and at 0.3 wt% of the modified modifier.
• Table 1 shows the composition, properties, and properties of the propeller type fan manufactured from the composition.
• propeller type fans formed from the composite of this formulation exhibit a reduction in rotational creep properties (deformation). The cause is required for the reduction in rigidity.
• the propeller type fan formed from the composite of this formula causes a decrease in the rotational fracture strength. This is due to the increase in breakage due to the interfering action between glass fibers during molding.
• the propeller fan formed from the composite of this formula causes a decrease in the rotational cleaving characteristic. This is due to lack of rigidity.
• Example 3 70 1 0 2 0 0 .4 1 2 0 0 18.0 .0
• the long fiber-reinforced columnar body (D) is a modified polymer modified with an organic silane-based compound or an unsaturated carboxylic acid or an acid anhydride thereof.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Materials Engineering (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Reinforced Plastic Materials (AREA)
• Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
• Injection Moulding Of Plastics Or The Like (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 1994
  • 1994-06-16 JP JP6158112A patent/JPH083396A/ja active Pending
• 1995
  • 1995-05-09 EP EP95921144A patent/EP0714940B1/en not_active Expired - Lifetime
  • 1995-05-09 WO PCT/JP1995/001159 patent/WO1995034603A1/ja active IP Right Grant
  • 1995-06-09 DE DE69511828T patent/DE69511828T2/de not_active Expired - Lifetime
  • 1995-06-09 CN CN95190734A patent/CN1068358C/zh not_active Expired - Fee Related
  • 1995-06-09 KR KR1019960700810A patent/KR0182308B1/ko not_active Expired - Fee Related
  • 1995-06-13 TW TW084106019A patent/TW296356B/zh not_active IP Right Cessation

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